5-Spirocyclopropane Isoxazolidines as Versatile Intermediates in Organic Synthesis

The review outlines the various different azaheterocycles available from 5-spirocyclopropane isoxazolidines. These compounds can be regarded as versatile direct precursors of tetrahydro-, dihydropyridone and azetidinone derivatives. The current scope and limitations, and the selectivity aspects of the different processes are discussed therein.     

Solid-state interactions and drug release of teicoplanin in binary combinations with peracetylated α-, β-, and γ-cyclodextrins

Triacetyl α-cyclodextrin, triacetyl β-cyclodextrin and triacetyl γ-cyclodextrin were tested as possible hydrophobic carriers to prolong the release of hydrophilic teicoplanin (TCP). Physical–chemical characterization of individual components, drug-carrier physical mixtures at 0.5, 0.67 and 0.75 mass fraction of carrier, and the respective interaction products by kneading or evaporative crystallization under microwave irradiation was carried out using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). In vitro drug release in pH 7.4 phosphate buffer at 37 °C was determined by intrinsic dissolution rate (IDR) measurements on non disintegrating compressed discs. Solid-state interactions of TCP with triacetyl α-cyclodextrin by evaporative crystallization and kneading and with triacetyl β-cyclodextrin by evaporative crystallization (probably resulting in carrier amorphization) were demonstrated. The role of carrier hydrophobicity, carrier mass fraction and preparation method of solid drug-carrier combinations on solid-state drug-carrier interactions and slowing down of TCP release was assessed. Modulation of drug release can be achieved using TCP-triacetyl γ-cyclodextrin combinations at 0.5 mass fraction of carrier.     

Coordination properties of 6-deoxy-6-[1-(2-amino) ethylamino]-β-cyclodextrin and the ability of its copper(II) complex to recognize and separate amino acid enantiomeric pairs

The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]--cyclodextrin was synthesized, and an NMR, EPR, pH-metric, and calorimetric investigation was carried out in aqueous solution in order to ascertain its behaviour towards protonation and copper(II) complex formation. The thermodynamic parameters of the ternary complex formation with alanine, phenylalanine and tryptophan enantiomeric pairs were also determined (25° C andI=0.1 mol dm^–3). No thermodynamic enantioselectivity was observed in these systems, while a chiral, though poor, discrimination was observed in LEC: c.d. spectra also show enantiomeric stereoselectivity. The results of the present investigation, compared with previously reported results, suggest the occurence of acis-complex trans-complex equilibrium in such systems.     

alpha-(Arylthio)imidoyl Radicals: [3 + 2] Radical Annulation of Aryl Isothiocyanates with 2-Cyano-Substituted Aryl Radicals

A novel cascade radical reaction is described involving aryl isothiocyanates and 2-cyanoaryl radicals. The mechanism entails the formation of an alpha-(arylthio)imidoyl radical, a 5-exo-dig cyclization onto a cyano group, and a final 6-membered ring closure of an iminyl radical. The competitive 5-membered spiro-cyclization of the iminyl, leading to an isomeric product, was only observed in the case of a disubstituted aryl isothiocyanate. The whole process involves a rare example of [3 + 2] radical annulation and allows the one-pot synthesis of tetracondensed nitrogen heterocycles in good yields.     

Information-theoretic differential geometry of quantum phase transitions

The manifold of coupling constants parametrizing a quantum Hamiltonian is equipped with a natural Riemannian metric with an operational distinguishability content. We argue that the singularities of this metric are in correspondence with the quantum phase transitions featured by the corresponding system. This approach provides a universal conceptual framework to study quantum critical phenomena which is differential geometric and information theoretic at the same time.     

A Cationic Zinc Hydride Cluster Stabilized by an N‐Heterocyclic Carbene: Synthesis,Reactivity, and Hydrosilylation Catalysis

The trinuclear cationic zinc hydride cluster [(IMes)₃Zn₃H₄(THF)](BPh₄)₂ ( 1 ) was obtained either by protonation of the neutral zinc dihydride [(IMes)ZnH₂]₂ with a Brønsted acid or by addition of the putative zinc dication [(IMes)Zn(THF)]²⁺. A triply bridged thiophenolato complex 2 was formed upon oxidation of 1 with PhS? SPh. Protonolysis of 1 by methanol or water gave the corresponding trinuclear dicationic derivatives. At ambient temperature, 1 catalyzed the hydrosilylation of aldehydes, ketones, and nitriles. Carbon dioxide was also hydrosilylated under forcing conditions when using (EtO)₃SiH, giving silylformate as the main product.     

Un'estensione del teorema di dualità di Poincaré

Riassunto In questo lavoro si generalizza la dualità di Poincaré a spazi topologici localmente omeomorfi con insiemi analitici realin-dimensionali con singolarità isolate; tali spazi non sono in generale orientabili, nè sono muniti di una struttura analitica globale. Rispetto ad un analogo risultato diL. Kaup ([6]), il nostro Teorema 2 si dimostra a prescindere dall'esistenza di normalizzazioni topologiche (nel senso di [6]).

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Summary In this paper we generalize Poincaré duality to topological spaces locally homeomorphic with real analyticn-dimensional sets with isolated singularities; these spaces are in general neither orientable nor globally analytic. Compared with a similar result ofL. Kaup ([6]), our Theorem 2 is proved without supposing the existence of a topological normalization (in the sense of [6]).

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Lavoro eseguito come borsista del C.N.R. nell'ambito del G.N.S.A.G.A.     

A One-Pot Entry to a Novel 3-H-benzo[d]pyrazolo[1,5-b]isothiazole Ring System

Summary The phosphorus ylide obtained from the reaction between 2-aminobenzo[d]isothiazol-3-one and dimethyl acetylenedicarboxylate in the presence of triphenylphosphine undergoes a smooth intramolecular Wittig-type reaction to produce, in a one-pot reaction, 3-H-benzo[d]pyrazolo[1,5-b]isothiazole-2,3a-dicarboxylic acid dimethyl ester, a novel functionalized heterocyclic compound.     

A UV-Visible/Raman spectroelectrochemical study of the stability of poly(3,4-ethylendioxythiophene) films

Poly(3,4-ethylendioxythiophene) films were electropolymerized in aqueous medium without using any surfactant, on glassy carbon electrodes. UV/Vis and Raman spectroelectrochemical techniques were used to analyze the degradation of the polymer film occurring at different pH values. Spectroelectrochemistry has proven to be a very useful analytical tool for this purpose, thanks to its ability to provide information not only about the extent of degradation, but also about mechanistic aspects of the process. From our results we extracted important information about the main factors that play a role in the degradation, in particular about the influence of repetitive doping and de-doping cycles and of photo-induced processes, as a function of the characteristics of the solution, i.e. of pH.     

Beta-functionalised polythiophenes as microelectrode modifiers in low conductive media

A study on polythiophene coated microelectrodes is reported, the goal being that of checking the capability of these electrochemical systems to work in low conductive media. The possibility of electrochemically p-doping the polymer in the presence of very low concentrations or even in the absence of supporting electrolyte in the solution is ascertained, opening the way to the use of similar systems in pure solvent media. This result is obtained in such conditions that the presence of residual charges--and corresponding counterions--trapped inside the film coating can be reasonably hypothesised.